Rapid reduction and reemission of mercury deposited into snowpacks during atmospheric mercury depletion events at churchill, Manitoba, Canada

Mercury (Hg) in some Arctic marine mammals has increased to levels that may be toxic to Northern peoples consuming them as traditional food. It has been suggested that sunlight-induced atmospheric reactions called springtime atmospheric Hg depletion events (AMDEs) result in the loading of -150-300 tons of Hg to the Canadian Arctic archipelago each spring and that AMDEs are the ultimate source of Hg to Arctic foodwebs. AMDEs result from the oxidation of gaseous elemental Hg0 (GEM) in Arctic atmospheres to reactive gaseous Hg (RGM) and particulate Hg (pHg), both of which fall out of the atmosphere to snowpacks. We studied the springtime cycling of Hg between air and snowpacks near Churchill, Manitoba, for 2 years to determine the net input of Hg to Hudson Bay from AMDEs. In 2004, we monitored atmospheric concentrations of GEM, pHg, and RGM while simultaneously measuring concentrations of total Hg (THg) in surface snow collected over the sea ice on Hudson Bay. During numerous springtime AMDEs, concentrations of THg in surface snow increased, often to over 60 ng/L, demonstrating that AMDEs resulted in deposition of oxidized Hg (Hg(II)) to snowpacks. However, immediatelyfollowing AMDEs, average concentrations of THg in snow declined drastically from between 67.8+/-7.7 ng/L during AMDEs to only 4.25+/-1.85 ng/L four or more days following them. In 2003, we measured THg in surface snow collected daily over the sea ice and total gaseous Hg (TGM) concentrations in the interstitial airspaces of snowpacks. When concentrations of THg in the surface snow decreased, concentrations of TGM in interstitial airspaces of the snowpack increased sharply from between approximately 1.4-3.4 ng/m(3) to between approximately 20-150 ng/m(3), suggesting thatthere was a reduction of deposited Hg(II) to GEM, which then diffused out of snowpacks. At snowmelt in both 2003 and 2004, average concentrations of THg in meltwater collected over Hudson Bay were only 4.04+/-2.01 ng/L. Using concentrations of THg in meltwater and snow water equivalent, we estimated a net springtime loading of only 2.1+/-1.7 mg/ha of Hg to Hudson Bay from AMDEs, indicating that only a small portion of the Hg(II) deposited during AMDEs enters Hudosn Bay each spring.     

Dynamic oxidation of gaseous mercury in the Arctic troposphere at polar sunrise

Gaseous elemental mercury (Hg0) is a globally distributed air toxin with a long atmospheric residence time. Any process that reduces its atmospheric lifetime increases its potential accumulation in the biosphere. Our data from Barrow, AK, at 71 degrees N show that rapid, photochemically driven oxidation of boundary-layer Hg0 after polar sunrise, probably by reactive halogens, creates a rapidly depositing species of oxidized gaseous mercury in the remote Arctic troposphere at concentrations in excess of 900 pg m(-3). This mercury accumulates in the snowpack during polar spring at an accelerated rate in a form that is bioavailable to bacteria and is released with snowmelt during the summer emergence of the Arctic ecosystem. Evidence suggests that this is a recent phenomenon that may be occurring throughout the earth's polar regions.     

Measurements of atmospheric mercury species at a coastal site in the Antarctic and over the south Atlantic Ocean during polar summer

Mercury and many of its compounds behave exceptionally in the environment because of their volatility, capability for methylation, and subsequent biomagnification in contrast with most of the other heavy metals. Long-range atmospheric transport of elemental mercury, its transformation to more toxic methylmercury compounds, the ability of some to undergo photochemical reactions, and their bioaccumulation in the aquatic food chain have made it a subject of global research activities, even in polar regions. The first continuous high-time-resolution measurements of total gaseous mercury in the Antarctic covering a 12-month period were carried out at the German Antarctic research station Neumayer (70 degrees 39' S, 8 degrees 15' W) between January 2000 and February 2001. We recently reported that mercury depletion events (MDEs) occur in the Antarctic after polar sunrise, as was previously shown for Arctic sites. These events (MDEs) end suddenly during Antarctic summer. A possible explanation of this phenomenon is presented in this paper, showing that air masses originating from the sea-ice surface were a necessary prerequisite for the observations of depletion of atmospheric mercury at polar spring. Our extensive measurements at Neumayer of atmospheric mercury species during December 2000-February 2001 show that fast oxidation of gaseous elemental mercury leads to variable Hg0 concentrations during Antarctic summer, accompanied by elevated concentrations, up to more than 300 pg/m3, of reactive gaseous mercury. For the first time in the Southern Hemisphere, atmospheric mercury species measurements were also performed onboard of a research vessel, indicating the existence of homogeneous background concentrations over the south Atlantic Ocean. These new findings contain evidence for an enhanced oxidizing potential of the Antarctic atmosphere over the continent that needs to be considered for the interpretation of dynamic transformations of mercury during summertime.     

Concentration and dry deposition of mercury species in arid south central New Mexico (2001-2002)

This research was initiated to characterize atmospheric deposition of reactive gaseous mercury (RGM), particulate mercury (HgP; <2.5 microm), and gaseous elemental mercury (Hg0) in the arid lands of south central New Mexico. Two methods were field-tested to estimate dry deposition of three mercury species. A manual speciation sampling train consisting of a KCl-coated denuder, 2.5 microm quartz fiber filters, and gold-coated quartz traps and an ion-exchange membrane (as a passive surrogate surface) were deployed concurrently over 24-h intervals for an entire year. The mean 24-h atmospheric concentration for RGM was 6.8 pg m(-3) with an estimated deposition of 0.10 ng m(-2) h(-1). The estimated deposition of mercury to the passive surrogate surface was much greater (4.0 ng m(-2) h(-1)) but demonstrated a diurnal pattern with elevated deposition from late afternoon to late evening (1400-2200; 8.0 ng m(-2) h(-1)) and lowest deposition during the night just prior to sunrise (2200-0600; 1.7 ng m(-2) h(-1)). The mean 24-h atmospheric concentrations for HgP and Hg0 were 1.52 pg m(-3) and 1.59 ng m(-3), respectively. Diurnal patterns were observed for RGM with atmospheric levels lowest during the night prior to sunrise (3.8 pg m(-3)) and greater during the afternoon and early evening (8.9 pg m(-3)). Discernible diurnal patterns were not observed for either HgP or Hg0. The total dry deposition of Hg was 5.9 microg m-2 year-' with the contribution from the three species as follows: RGM (0.88 microg m(-2) year(-1)), HgP (0.025 microg m(-2) year(-1)), and Hg0 (5.0 microg m(-2) year(-1)). The annual wet deposition for total mercury throughout the same collection duration was 4.2 microg m(-2) year (-1), resulting in an estimated total deposition of 10.1 microg m(-2) year(-1) for Hg. On one sampling date, enhanced HgP (12 pg m(-3)) was observed due to emissions from a wildfire approximately 250 km to the east.     

Sources of speciated atmospheric mercury at a residential neighborhood impacted by industrial sources

Speciated measurements of atmospheric mercury plumes were obtained at an industrially impacted residential area of East St. Louis, IL. These plumes were found to result in extremely high mercury concentrations at ground level that were composed of a wide distribution of mercury species. Ground level concentrations as high as 235 ng m(-3) for elemental mercury (Hg0) and 38 300 pg m(-3) for reactive mercury species (reactive gaseous (RGM) plus particulate (PHg) mercury) were measured. The highest mercury concentrations observed during the study were associated with plumes that contained high concentrations of all mercury species (Hg0, RGM, and PHg) and originated from a source located southwest of the sampling site. Variations in proportions of Hg0/RGM/PHg among plumes, with Hg0 dominating some plumes and RGM and/or PHg dominating others, were attributed to differences in emissions from different sources. Correlations between mercury plumes and elevated NO(x) were not observed; however, a correlation between elevated SO2 and mercury plumes was observed during some but not all plume events. Despite the presence of six coal-fired power plants within 60 km of the study site, wind direction data along with Hg/SO2 and Hg/NO(x) ratios suggest that high-concentration mercury plumes impacting the St. Louis-Midwest Particle Matter Supersite are attributable to local point sources within 5 km of the site.     

Atmospheric mercury (Hg) in the Adirondacks: concentrations and sources

Hourly averaged gaseous elemental Hg (GEM) concentrations and hourly integrated reactive gaseous Hg (RGM), and particulate Hg (Hg(p)) concentrations in the ambient air were measured at Huntington Forest in the Adirondacks, New York from June 2006 to May 2007. The average concentrations of GEM, RGM, and Hg(p) were 1.4 +/- 0.4 ng m(-3), 1.8 +/- 2.2 pg m(-3), and 3.2 +/- 3.7 pg m(-3), respectively. RGM represents < 3.5% of total atmospheric Hg or total gaseous Hg (TGM: GEM + RGM) and Hg(p) represents < 3.0% of the total atmospheric Hg. The highest mean concentrations of GEM, RGM, and Hg(p) were measured during winter and summer whereas the lowest mean concentrations were measured during spring and fall. Significant diurnal patterns were apparent in warm seasons for all species whereas diurnal patterns were weak in cold seasons. RGM was better correlated with ozone concentration and temperature in both warm (rho (RGM - ozone) = 0.57, p < 0.001; rho (RGM - temperature) = 0.62, p < 0.001) and cold seasons (rho (RGM - ozone) = 0.48, p = 0.002; rho (RGM - temperature) = 0.54, p = 0.011) than the other species. Potential source contribution function (PSCF) analysis was applied to identify possible Hg sources. This method identified areas in Pennsylvania, West Virginia, Ohio, Kentucky, Texas, Indiana, and Missouri, which coincided well with sources reported in a 2002 U.S. mercury emissions inventory.     

Development and characterization of an annular denuder methodology for the measurement of divalent inorganic reactive gaseous mercury in ambient air

Atmospheric mercury is predominantly present in the gaseous elemental form (Hg0). However, anthropogenic emissions (e.g., incineration, fossil fuel combustion) emit and natural processes create particulate-phase mercury(Hg(p)) and divalent reactive gas-phase mercury (RGM). RGM species (e.g., HgCl2, HgBr2) are water-soluble and have much shorter residence times in the atmosphere than Hg0 due to their higher removal rates through wet and dry deposition mechanisms. Manual and automated annular denuder methodologies, to provide high-resolution (1-2 h) ambient RGM measurements, were developed and evaluated. Following collection of RGM onto KCl-coated quartz annular denuders, RGM was thermally decomposed and quantified as Hg0. Laboratory and field evaluations of the denuders found the RGM collection efficiency to be >94% and mean collocated precision to be <15%. Method detection limits for sampling durations ranging from 1 to 12 h were 6.2-0.5 pg m(-3), respectively. As part of this research, the authors observed that methods to measure Hg(p) had a significant positive artifact when RGM coexists with Hg(p). This artifact was eliminated if a KCl-coated annular denuder preceded the filter. This new atmospheric mercury speciation methodology has dramatically enhanced our ability to investigate the mechanisms of transformation and deposition of mercury in the atmosphere.     

Mercury in the atmosphere, snow and melt water ponds in the North Atlantic Ocean during Arctic summer

Atmospheric mercury speciation measurements were performed during a 10 week Arctic summer expedition in the North Atlantic Ocean onboard the German research vessel RV Polarstern between June 15 and August 29, 2004. This expedition covered large areas of the North Atlantic and Arctic Oceans between latitudes 54 degrees N and 85 degrees N and longitudes 16 degrees W and 16 degrees E. Gaseous elemental mercury (GEM), reactive gaseous mercury (RGM) and mercury associated with particles (Hg-P) were measured during this study. In addition, total mercury in surface snow and meltwater ponds located on sea ice floes was measured. GEM showed a homogeneous distribution over the open North Atlantic Ocean (median 1.53 +/- 0.12 ng/m3), which is in contrast to the higher concentrations of GEM observed over sea ice (median 1.82 +/- 0.24 ng/m3). It is hypothesized that this results from either (re-) emission of mercury contained in snow and ice surfaces that was previously deposited during atmospheric mercury depletion events (AMDE) in the spring or evasion from the ocean due to increased reduction potential at high latitudes during Arctic summer. Measured concentrations of total mercury in surface snow and meltwater ponds were low (all samples <10 ng/L), indicating that marginal accumulation of mercury occurs in these environmental compartments. Results also reveal low concentrations of RGM and Hg-P without a significant diurnal variability. These results indicate that the production and deposition of these reactive mercury species do not significantly contribute to the atmospheric mercury cycle in the North Atlantic Ocean during the Arctic summer.     

Antarctic springtime depletion of atmospheric mercury

Unlike other heavy metals that are inherently associated with atmospheric aerosols, mercury in ambient air exists predominantly in the gaseous elemental form. Because of its prolonged atmospheric residence time, elemental mercury vapor is distributed on a global scale. Recently, Canadian researchers have discovered that total gaseous mercury levels in the lower tropospheric boundary layer in the Canadian Arctic are often significantly depleted during the months after polar sunrise. A possible explanation may involve oxidation of elemental mercury, followed by adsorption and deposition of the oxidized form, leading to an increased input of atmospheric mercury into the Arctic ecosystem. Here we present the first continuous high-time-resolution measurements of total gaseous mercury in the Antarctic covering a 12-month period between January 2000 and January 2001 at the German Antarctic research station Neumayer (70 degrees 39' S, 8 degrees 15' W). We report that mercury depletion events also occur in the Antarctic after polar sunrise and compare our measurements with a data setfrom Alert, Nunavut, Canada. We also present indications that BrO radicals and ozone play a key role in the boundary-layer chemistry during springtime mercury depletion events in the Antarctic troposphere.     

Atmospheric mercury speciation: laboratory and field evaluation of a mist chamber method for measuring reactive gaseous mercury

Knowledge of atmospheric mercury speciation is critical to modeling its fate. Thus there is a crucial need for reliable methods to measure the fraction of gaseous atmospheric Hg which is in the oxidized Hg(II) form (termed reactive gaseous mercury, RGM). We have developed a novel method for measurement of RGM using a refluxing mist chamber, and we recently reported the results of sampling campaigns for RGM in Tennessee and Indiana. In general, measured RGM levels were about 3% of total gaseous mercury (TGM), and our results support prevailing hypotheses about the nature and behavior of RGM in ambient air. Because its use for RGM is growing, we now report in more detail the development and testing of the mist chamber method. Several styles of mist chambers have been investigated. The most versatile design employs a single nebulizer nozzle and can operate at flows of 15-20 L/min. The water-soluble Hg is collected in ca. 20 mL of absorbing solution, which is then analyzed for Hg(II) by SnCl2 reduction and CVAFS. One-hour samples (ca. 1 m3 of air) generally contain 50-200 pg of RGM. The method detection limit for 1-h samples is approximately 6-10 pg/m3. Thus short sample times can reveal temporal variations in RGM that would not otherwise be observable. The efficiency of collecting RGM in mist chambers is highly dependent on Cl- concentration in the absorbing solution, in keeping with equilibrium calculations. Artifact formation of Hg(II) by oxidation of Hg0 under ozone ambient conditions appears to be sufficiently slow so as to be negligible for the short (ca. 1 h) runs that are typically employed. We observed no significant error from cosampled particles or aerosols in rural nonimpacted air samples. We have developed a simple approach to analyzing mist chamber samples in the field using an automated Hg sampler.     

Modern and historic atmospheric mercury fluxes in northern Alaska: Global sources and Arctic depletion

We reconstruct from lake-sediment archives atmospheric Hg deposition to Arctic Alaska over the last several centuries and constrain a contemporary lake/watershed mass-balance with real-time measurement of Hg fluxes in rainfall, runoff, and evasion. Results indicate that (a) anthropogenic Hg impact in the Arctic is of similar magnitude to that at temperate latitudes; (b) whole-lake Hg sedimentation determined from 55 210Pb-dated cores from the five small lakes demonstrates a 3-fold increase in atmospheric Hg deposition since the advent of the Industrial Revolution; (c) because of high soil Hg concentrations and relatively low atmospheric deposition fluxes, erosional inputs to these lakes are more significant than in similar temperate systems; (d) volatilization accounts for about 20% of the Hg losses (evasion and sedimentation); and (e) another source term is needed to balance the evasional and sedimentation sinks. This additional flux (1.21+/-0.74 microg m(-2) yr(-1)) is comparable to direct atmospheric Hg deposition and may be due to some combination of springtime Arctic depletion and more generalized deposition of reactive gaseous Hg species.     

Automated speciated mercury measurements in Michigan

Automated speciated mercury measurements were made at a rural (Dexter, MI) and an urban (Detroit, MI) site in Michigan during selected times from 1999 to 2002 to assess the concentrations of elemental (Hg0), reactive gaseous (RGM), and particulate mercury (Hgp) in these environments. Here we present the first-ever reported values for RGM in Michigan. Median RGM concentrations were 2.21-2.93 pg m(-3) at Dexter and were 3-11 times higher in Detroit at 6.41-22.0 pg m(-3). Maximum RGM concentrations of 38.7 pg m(-3) and 270 pg m(-3) were observed in Dexter and Detroit, respectively. Measured RGM/Hg0 ratios were in the range of 0.04-11.60% indicating that at times RGM comprises greater than the currently held view of 5% of total gaseous mercury in the air. Well-pronounced diurnal patterns of RGM were observed at the rural site, whereas the urban site exhibited patterns that were influenced by nighttime emissions and regional transport. An analysis of RGM/Hgp ratios at the urban site when combined with trajectory analysis suggests that the site receives mercury inputs from both local and regional sources. Episodes of elevated ozone concentrations which were accompanied by increases in RGM concentrations were observed to occur in the late afternoon and overnight. These may be evidence of advection of ozone and RGM over long distances to the site.     

Modeling dynamic exchange of gaseous elemental mercury at polar sunrise

At polar sunrise, gaseous elemental mercury (GEM) undergoes an exceptional dynamic exchange in the air and at the snow surface during which GEM can be rapidly removed from the atmosphere (the so-called atmospheric mercury depletion events (AMDEs)) as well as re-emitted from the snow within a few hours to days in the Polar Regions. Although high concentrations of total mercury in snow following AMDEs is well documented, there is very little data available on the redox transformation processes of mercury in the snow and the fluxes of mercury at the air/snow interface. Therefore, the net gain of mercury in the Polar Regions as a result of AMDEs is still an open question. We developed a new version of the global mercury model, GRAHM, which includes for the first time bidirectional surface exchange of GEM in Polar Regions in spring and summer by developing schemes for mercury halogen oxidation, deposition, and re-emission. Also for the first time, GOME satellite data-derived boundary layer concentrations of BrO have been used in a global mercury model for representation of halogen mercury chemistry. Comparison of model simulated and measured atmospheric concentrations of GEM at Alert, Canada, for 3 years (2002-2004) shows the model's capability in simulating the rapid cycling of mercury during and after AMDEs. Brooks et al. (1) measured mercury deposition, reemission, and net surface gain fluxes of mercury at Barrow, AK, during an intensive measurement campaign for a 2 week period in spring (March 25 to April 7, 2003). They reported 1.7, 1.0 +/- 0.2, and 0.7 +/- 0.2 microg m(-2) deposition, re-emission, and net surface gain, respectively. Using the optimal configuration of the model, we estimated 1.8 microg m(-2) deposition, 1.0 microg m(-2) re-emission, and 0.8 microg m(-2) net surface gain of mercury for the same time period at Barrow. The estimated net annual accumulation of mercury within the Arctic Circle north of 66.5 degrees is approximately 174 t with +/-7 t of interannual variability for 2002-2004 using the optimal configuration. We estimated the uncertainty of the model results to the Hg/Br reaction rate coefficient to be approximately 6%. Springtime is clearly demonstrated as the most active period of mercury exchanges and net surface gain (approximately 46% of annual accumulation) in the Arctic.     

Ambient mercury sources in Rochester, NY: results from Principle Components Analysis (PCA) of Mercury Monitoring Network Data

Continuous atmospheric measurements of speciated mercury (Hg) (elemental mercury (Hg?), reactive gaseous mercury (RGM), and particulate mercury (Hgp)) were made in Rochester, NY from Dec 2007 to May 2009. Continuous measurements of ozone (O?), sulfur dioxide (SO?), carbonmonoxide (CO), particulate matter (PM?.?), and meteorological data were also available. A principle components analysis (PCA) of 3886 observations of 13 variables for the period identified six major factors. Melting snow was observed to be a source of Hg?in winters. Positive correlations between RGM and O? in the spring and summer may be indicative of Hg? oxidation. RGM concentrations increased simultaneously with SO? suggesting the influence of coal fired power plants (CFPP). The ?fth factor (F5) containing O? (high negative loading), CO (positive loading), Hg? and Hg(p) (positive), and/or RGM (negative) was identified as a mobile source which was usually observed during morning rush hours (6:00-9:00 a.m.). The concentrations of the three mercury species from the direction of the CFPP were significantly reduced following the shutdown of this source.     

Enhanced deposition and bioaccumulation of mercury in Antarctic terrestrial ecosystems facing a coastal polynya

Mercury emitted by anthropogenic and natural sources occurs in the atmosphere mostly in the gaseous elemental form, which has a long lifetime in tropical and temperate regions. Once deposited in terrestrial and aquatic ecosystems the metal is partly re-emitted into the air, thus assuming the characteristics of global pollutants such as persistent volatile chemicals. In polar regions, during and after the sunrise, the photochemically driven oxidation of gaseous Hg by reactive halogens may result in areas of greatly enhanced Hg deposition. Mercury concentrations in soils, lichens, and mosses collected in a stretch between 74 degrees 30' S and 76 degrees 00' S, in ice-free coastal areas of Victoria Land facing the Terra Nova Bay coastal polynya, were higher than typical Antarctic baselines. The finding of enhanced Hg bioaccumulation in Antarctic terrestrial ecosystems facing a coastal polynya strongly supports recent speculations on the role of ice crystals ("frost flowers") growing in polynyas as a dominant source of sea salt aerosols and bromine compounds, which are involved in springtime mercury depletion events (MDEs). These results raise concern aboutthe possible environmental effects of changes in regional climate and sea ice coverage, and on the possible role of Antarctica as a sink in the mercury cycle.     

Measurements of mercury in dew: atmospheric removal of mercury species to a wetted surface

The importance of dew in the mercury cycle was investigated during three sampling periods in the Great Lakes region and one in the Florida Everglades. Mercury concentrations ranged from 1.0 to 22.6 ng/L in dew. Deposition per dew event was, on average, lowest at a remote site on Lake Superior (0.31 ng/m2) and highest in the Florida Everglades (1.4 ng/m2). The estimated mercury deposition to the canopy associated with dew approximately equaled that of precipitation during the wintertime Everglades study. Relative to other trace elements (Mg, Ti, V, Mn, Ni, Cu, As, Sr, Cd, Sb, La, Ce, Pb), mercury was found to be more enriched in rain than dew, suggesting the importance of gas scavenging for precipitation. The fraction of mercury in dew from particulate deposition was estimated to average 40%, with the remaining contribution from reactive gaseous Hg (RGM). RGM, for which little reliable data exists, was measured in the Everglades and was significantly reduced at the start of a dew event, indicating pronounced removal of this soluble mercury species to wetted surfaces. The first estimates of RGM deposition velocities based on mercury flux measurements are reported here and range up to 1.6 cm/s.     

Estimation of dry deposition of atmospheric mercury in Nevada by direct and indirect methods

Atmospheric models and limited measurements indicate that dry deposition of atmospheric mercury is an important process by which mercury is input to ecosystems. To begin to fill the measurement data gap, multiple methods were used simultaneously during seasonal campaigns conducted in 2005 and 2006 to estimate dry deposition of atmospheric mercury at two Mercury Deposition Network (MDN) sites in rural Nevada and in Reno, Nevada. Gaseous elemental mercury (Hg0), reactive gaseous mercury (RGM), and particulate-bound mercury (Hgp) concentrations were measured using Tekran 2537A/1130/ 1135 systems. These speciated measurements were combined with on-site meteorological measurements to estimate depositional fluxes of RGM and Hgp using dry deposition models. Modeled fluxes were compared with more direct measurements obtained using polysulfone cation-exchange membranes and foliar surfaces. Dynamic flux chambers were used to measure soil mercury exchange. RGM concentrations were higher during warmer months at all sites, leading to seasonal variation in the modeled importance of RGM as a component of total depositional load. The ratio of dry to wet deposition was between 10 and 90%, and varied with season and with the methods used for dry deposition approximations. This work illustrates the variability of mercury dry deposition with location and time and highlights the need for direct dry deposition measurements.     

Diurnal cycles of gaseous mercury within the snowpack at Kuujjuarapik/Whapmagoostui,Québec,Canada

Mercury is a globally dispersed and toxic pollutant that can be transported far from its emission sources. In polar and subpolar regions, recent research activities have demonstrated its ability to be converted and deposited rapidly onto snow surfaces during the so-known Mercury Depletion Events (MDEs). The fate of mercury once deposited onto snow surfaces is still unclear: a part could be re-emitted to the atmosphere, the other part could contaminate water systems at the snowmelt. Its capacity to transform to more toxic form and to bioaccumulate in the food chain has consequently made mercury a threat for Arctic ecosystems. The snowpack is a medium that greatly interacts with a variety of atmospheric gases. Its role in the understanding of the fate of deposited mercury is crucial though it is poorly understood. In April 2002, we studied an environmental component of mercury, which is interstitial gaseous mercury (IGM) present in the air of the snowpack at Kuujjuarapik/Whapmagoostui (55 degrees N, 77 degrees W), Canada on the east shore of the Hudson Bay. We report here for the first time continuous IGM measurements at various depths inside a seasonal snowpack. IGM concentrations exhibit a well-marked diurnal cycle with uninterrupted events of Hg0 depletion and production within the snowpack. A possible explanation of Hg0 depletion within the snowpack may be Hg0 oxidation processes. Additionally, we assume that the notable production of Hg0 during the daytime may be the results of photoreduction and photoinitiated reduction of Hg(II) complexes. These new observations show that the snowpack plays undoubtedly a role in the global mercury cycle.     

Methylated mercury species in Canadian high Arctic marine surface waters and snowpacks

We sampled seawater and snowpacks in the Canadian high Arctic for methylated species of mercury (Hg). We discovered that, although seawater sampled under the sea ice had very low concentrations of total Hg (THg, all forms of Hg in a sample; on average 0.14-0.24 ng L(-1)), 30-45% of the THg was in the monomethyl Hg (MMHg) form (on average 0.057-0.095 ng L(-1)), making seawater itself a direct source of MMHg for biomagnification through marine food webs. Seawater under the ice also contained high concentrations of gaseous elemental Hg (GEM; 129 +/- 36 pg L(-1)), suggesting that open water regions such as polynyas and ice leads were a net source of approximately 130 +/- 30 ng Hg m(-2) day(-1) to the atmosphere. We also found 11.1 +/- 4.1 pg L(-1) of dimethyl Hg (DMHg) in seawater and calculated that there could be a significant flux of DMHg to the atmosphere from open water regions. This flux could then resultin MMHg deposition into nearby snowpacks via oxidation of DMHg to MMHg in the atmosphere. In fact, we found high concentrations of MMHg in a few snowpacks near regions of open water. Interestingly, we discovered a significant log-log relationship between Cl- concentrations in snowpacks and concentrations of THg. We hypothesize that as Cl- concentrations in snowpacks increase, inorganic Hg(II) occurs principally as less reducible chloro complexes and, hence, remains in an oxidized state. As a result, snowpacks that receive both marine aerosol deposition of Cl- and deposition of Hg(II) via springtime atmospheric Hg depletion events, for example, may contain significant loads of Hg(II). Overall, though, the median wet/dry loads of Hg in the snowpacks we sampled in the high Arctic (5.2 mg THg ha(-1) and 0.03 mg MMHg ha(-1)) were far below wet-only annual THg loadings throughout southern Canada and most of the U.S. (22-200 mg ha(-1)). Therefore, most Arctic snowpacks contribute     

Dark oxidation of dissolved gaseous mercury in polar ice mimics

The low-temperature chemistry associated with environmentally available mercury has recently attracted considerable scientific interest due to the discovery of systemic gas-phase mercury depletion events (MDEs) which occur periodically at the poles. However, the fate of the mercury once it enters the snowpack is not fully understood, even its chemical speciation has yet to be well characterized. An issue that is of particular concern in frozen environments is the transformation of elemental mercury (Hg(0)) to more bioavailable oxidized forms, which can then be methylated by biotic and abiotic processes. The resulting methyl mercury species produced can bioaccumulate through the food chain and the health effects of this on humans and mammals have been well-documented. During the current study, a novel set of "freeze-induced" pathways, which can potentially affect the reactivity of dissolved gaseous mercury (DGM) were followed. The experiments were performed using environmentally relevant cosolutes at appropriate concentration levels and temperatures. Evidence is thereby presented that due to rate accelerations associated with the operation of the freeze-concentration effect, DGM is oxidized to Hg(2+) ions when frozen in the presence of a variety of materials including hydrogen peroxide, nitrous acid and the sulfuric acid/O(2) couple.